Detergent and dispersant compositions from high temperature polymerization products

ABSTRACT

High temperature polymerization process and products obtained therefrom are provided. The polymerization is conducted at above 225° C. to produce polymers having a degree of polymerization below 50. The products are useful as detergent additives and for subsequent polymerization.

This is a continuation of application Ser. No. 08/467,686, filed Jun 6,1995 now abandoned which is a divisional of application Ser. No.08/258,300, filed Jun. 13, 1994, abandoned.

This invention relates to a DETERGENT AND DISPERSANT COMPOSITIONS FROMhigh temperature polymerization products. In particular, this inventionrelates to a high temperature polymerization process to produceoligomers. More particularly, this invention relates to a hightemperature polymerization process to produce terminally unsaturatedoligomers. Oligomers, as used herein and in the appended claims, refersto polymers having degree of polymerization of below 50.

Low molecular weight polymers are known to be useful detergentadditives, anti-redeposition agents, hard surface cleaners, scaleinhibitors, pigment dispersants, mineral dispersants, clay dispersants,water treatment additives and the like. However, production of very lowmolecular weight polymers of carboxylic monomers, especially acrylicacid, has proven to be a difficult task.

In certain applications, such as detergent additives, it is becomingincreasingly important that the carboxylic acid polymers arebiodegradable. It is known that biodegradability increases as molecularweight decreases. Therefore, processes which produce very low molecularweight polymers may provide routes to biodegradable polymer products.

The art has long sought an inexpensive, efficient and environmentallysound way to produce low molecular weight polymers.

One method of achieving low molecular weight polymers is through the useof efficient chain transfer agents, but this approach has severaldrawbacks. This approach incorporates the structure of the chaintransfer agent into the polymer chain. This can be undesirable sincethat structure will have an increasing effect on the properties of thepolymer as molecular weight decreases. Furthermore, the chain transferagents commonly employed are mercaptans. These materials are expensiveand have objectionable odors associated with their presence. Othercommon chain transfer agents are hypophosphites, bisulfites andalcohols. These also add to the cost of the process, impartfunctionality to the polymer, can introduce salts into the product, andmay necessitate a product separation step.

Another way of lowering the molecular weight of the polymers produced isby increasing the amount of initiator. This approach adds considerablyto the cost of production and may result in polymer chain degradation,crosslinking, and high levels of unreacted initiator remaining in theproduct. In addition, high levels of initiator may also result in highlevels of salt by-products in the polymer mixture which is known to bedetrimental to performance in many applications. The same is true forchain stopping agents such as sodium metabisulfite. Among the preferredfree-radical initiators for aqueous polymerization is hydrogen peroxide.It is relatively inexpensive, has low toxicity, and does not producedetrimental salt by-products. However, hydrogen peroxide does notgenerally decompose efficiently at conventional polymerizationtemperatures and large amounts must normally be used to generate enoughradicals to carry out a polymerization.

High levels of metal ions together with high levels of initiator havealso been tried as a means for controlling molecular weight. Such anapproach is unsuitable for some products, such as water treatmentpolymers, which cannot tolerate metal ion contaminants in the polymerproduct. In addition, depending on the metal ions used, the product maybe discolored due to the presence of the metal ions.

In the European Polymer Journal, 1972, Vol. 8, pp. 321-328, Feitdescribes a multistep synthesis technique for preparing terminallyunsaturated oligomers. The process described therein requires abase-catalyzed addition of an acetic acid ester derivative to anactivated olefin, followed by hydrolysis of one ester group, followed bya Mannich reaction to introduce a terminal double bond. This three stepprocess is repeated to prepare a terminally unsaturated oligomer withone additional mer. This process suffers the drawback of being fairlycomplex, expensive and time-consuming.

The present invention seeks to overcome the problems associated with thepreviously known methods for preparing terminally unsaturated oligomers.

In a first aspect of the present invention, there is provided aterminally unsaturated oligomer of the formula: ##STR1## wherein N is aresidue of the formula ##STR2## wherein X₁ and X₂ are independentlyselected from the group consisting of H, NH₄, alkali metals and alkalineearth metals;

wherein M is the residue of a monoethylenically unsaturated monomer;

wherein m is 0 to 47;

wherein n is 2 to 50;

and wherein the sum of n and m is less than or equal to 50.

It is understood that the N and M residues in the terminally unsaturatedoligomer may be randomly arranged. In other words, adjacent theterminally unsaturated moiety may be either an N or an M residue; theresidue adjacent the residue adjacent the terminally unsaturated moietymay be either an N or an M residue, and so on.

In a second aspect of the present invention, there is provided anoligomer mixture, comprising:

(a) from 5 to 95 percent by weight of the oligomer mixture of terminallyunsaturated oligomers of the formula: ##STR3## wherein X₁ and X₂ areindependently selected from the group consisting of H, NH₄, alkalimetals and alkaline earth metals;

wherein n is 1;

(b) from 5 to 95 percent by weight of the oligomer mixture of terminallyunsaturated oligomers of the formula: ##STR4## wherein X₁ and X₂ areindependently selected from the group consisting of H, NH₄, alkalimetals and alkaline earth metals;

wherein M is the residue of a monoethylenically unsaturated monomer;

wherein m is 0 or 1;

wherein n is 1 or 2;

and wherein the sum of n and m is 2; and

(c) from 0 to 90 percent by weight of the oligomer mixture of terminallyunsaturated oligomers of the formula: ##STR5## wherein X₁ and X₂ areindependently selected from the group consisting of H, NH₄, alkalimetals and alkaline earth metals;

wherein M is the residue of a monoethylenically unsaturated monomer;

wherein m is 0 to 5;

wherein n is 3 to 10;

wherein the sum of n and m is less than or equal to 10;

and wherein the sum of (a), (b) and (c) is equal to 100 percent.

In a third aspect of the present invention, there is provided acontinuous process for preparing terminally unsaturated oligomerscomprising:

(a) forming a reaction mixture comprising

(i) from 0.5 to 99.95 percent by weight of the reaction mixture of atleast one monomer selected from the group consisting of acrylic acid andsalts thereof, and acrylic acid and salts thereof in combination with atleast one monoethylenically unsaturated monomer;

(ii) from 0.05 to 25 percent by weight based on the weight of the atleast one monomer of at least one free-radical initiator; and

(iii) optionally, from 0 to 99.5 percent by weight of the reactionmixture of at least one solvent;

(b) continuously passing the reaction mixture through a heated zonewherein the reaction mixture is maintained at a temperature of at least225° C. for from 0.1 seconds to 300 seconds to form terminallyunsaturated oligomers.

In a fourth aspect of the present invention, there is provided a polymerproduct comprising, as polymerized units, the terminally unsaturatedoligomers of the present invention.

In a fifth aspect of the present invention, there is provided adetergent composition comprising the terminally unsaturated oligomers ofthe present invention.

In a sixth aspect of the present invention, there is provided adetergent composition comprising a polymer product comprising, aspolymerized units, the terminally unsaturated oligomers of the presentinvention.

The acrylic acid used in the process of the present invention can beglacial acrylic acid or a solution of acrylic acid. Furthermore, theacrylic acid can be in the form of a salt such as an alkali metal salt,ammonium salt, alkaline earth metal salt or a combination thereof.Preferably, the acrylic acid is glacial acrylic acid or an aqueoussolution of acrylic acid. The acrylic acid is present in the reactionmixture at a level of from 0.5 to 99.95 percent by weight, preferablyfrom 1 to 95 percent by weight, most preferably from 5 to 90 percent byweight.

In addition to the acrylic acid, other monoethylenically unsaturatedmonomers may be used. Other suitable monoethylenically unsaturatedmonomers include other C₃ -C₆ monoethylenically unsaturatedmonocarboxylic acids, and the alkali metal alkaline earth metal andammonium salts thereof, such as, for example, methacrylic acid, crotonicacid, vinylacetic acid, and acryloxypropionic acid and salts thereof.Other suitable monoethylenically unsaturated monomers include C₄ -C₈monoethylenically unsaturated dicarboxylic acids and the alkali metaland ammonium salts thereof, and the anhydrides of the cis-dicarboxylicacids; such as, for example, maleic acid, maleic anhydride, itaconicacid, mesaconic acid, fumaric acid, citraconic acid, tetrahydrophthalicanhydrides, cyclohexene dicarboxylic acids and salts thereof. Othersuitable monoethylenically unsaturated monomers include acrylamide,t-butylacrylamide, N,N-dimethylacrylamide, and acrylonitrile. Othermonoethylenically unsaturated monomers include alkyl esters of acrylicor methacrylic acids such as methyl acrylate, ethyl acrylate, butylacrylate, methyl methacrylate, ethyl methacrylate, butyl methacrylateand isobutyl methacrylate; hydroxyalkyl esters of acrylic or methacrylicacids such as hydroxyethyl acrylate, hydroxypropyl acrylate,hydroxyethyl methacrylate, and hydroxypropyl methacrylate; acrylamide,methacrylamide, N-tertiarybutylacrylamide, N-methylacrylamide,dimethylaminopropylmethacrylamide; methacrylonitrile, allyl alcohol,allylsulfonic acid, allylphosphonic acid, vinylphosphonic acid,dimethylaminoethyl acrylate, dimethylaminoethyl methacrylate,phosphoethyl methacrylate, N-vinylpyrrolidone, N-vinylformamide,N-vinylimidazole, vinyl acetate, styrene, styrenesulfonic acid and itssalts, vinylsulfonic acid and its salts, and2-acrylamido-2-methylpropanesulfonic acid and its salts. When used, theother monoethylenically unsaturated monomers may be present in thereaction mixture at a level of from 0.05 to 99, preferably from 1 to 95,most preferably from 5 to 90.

The monoethylenically unsaturated monomers which are acids may be intheir acid forms or in the form of the alkali metal, alkaline earthmetal or ammonium salts of the acid, or a combination thereof. Suitablebases useful for neutralizing the monomer acids include sodiumhydroxide, ammonium hydroxide, and potassium hydroxide. The acidmonomers may be neutralized to a level of from 0 to 100 percent. Mostpreferably, the carboxylic acid monomers are used in the unneutralizedform, however, partial neutralization of the carboxylic acid monomersmay alleviate corrosion on parts of the reaction equipment. The monomersmay be neutralized prior to or during the oligomerization reaction. Theterminally unsaturated oligomer products are often particularly usefulin their partially or completely neutralized form. Partially neutralizedterminally unsaturated oligomers, will have the formulae shown above,and in the claims below wherein X₂ will be different among the mers ofthe terminally unsaturated oligomers.

Suitable initiators for the processes of the present invention are anyconventional free-radical initiators including, but are not limited to,hydrogen peroxide, certain alkyl hydroperoxides, dialkyl peroxides,peresters, percarbonates, persulfates, peracids, oxygen, ketoneperoxides, azo initiators and combinations thereof. Specific examples ofsome suitable initiators include hydrogen peroxide, oxygen, t-butylhydroperoxide, di-tertiary butyl peroxide, tertiary-amyl hydroperoxide,methylethyl ketone peroxide and combinations thereof. The initiators arenormally used in amounts of from 0.05 percent to 25 percent based on theweight of total polymerizable monomer. A preferred range is from 0.5 to20 percent by weight of the total polymerizable monomer.

The monomers are preferably polymerized as dilute solutions. Thereaction mixture may contain one or more solvents at a level of from 0to 99.5 percent by weight of the reaction mixture, preferably from 30 to97 percent by weight of the reaction mixture, and most preferably from50 to 95 percent by weight of the reaction mixture. As the relativeamount of one or more solvents in the reaction mixture decreases,particularly below 60 percent, the molecular weight and thepolydispersity (D) of the resulting oligomer mixture increases. Suitablesolvents for the process of the present invention are capable ofdissolving the one or more monomers and the oligomers formed therefrom.Suitable solvents for the present invention include, for example, water,acetone, methanol, isopropanol, propionic acid, acetic acid, methylethylketone, dimethylformamide, dimethylsulfoxide and combinations thereof.Water is the preferred solvent.

In the process of the present invention, the reaction mixture iscontinuously passed through a heated zone wherein the reaction mixtureis maintained at a temperature of at least 225° C. under elevatedpressure. Once the reaction mixture is formed, it is preferable to havethe passing reaction mixture reach the polymerization temperature asrapidly as possible. Preferably, the reaction mixture reaches thepolymerization temperature within 5 minutes, more preferably within 2minutes, most preferably within I minute. Prior to reaching the reactiontemperature, the reaction mixture may be at any suitable temperature,preferably at a temperature of from room temperature to 450° C., mostpreferably from a temperature of from 60° C. to 400° C. Theoligomerization is conducted at a temperature of at least 225° C., andis preferably conducted at a temperature in the range of from 250° C. to500° C., and most preferably at a temperature in the range of from 275°C. to 450° C. At temperatures below 225° C., the molecular weight of theoligomer increases and the relative amount of by-products, particularlynon-terminally unsaturated compounds, increases. The oligomerization atthese elevated temperatures is rapid. Thus, the reaction mixture can bemaintained at the polymerization temperature for as little as 0.1seconds, preferably from 0.5 seconds to 5 minutes, most preferably from1 second to 2 minutes. At extended periods of time at which the reactionmixture is exposed to the polymerization temperature, the yield ofterminally unsaturated oligomer decreases. However, extended periods atthe polymerization temperature have been found to have little effect onboth the conversion of monomer and the molecular weight of the productsformed.

The elevated temperatures of the polymerization require that thepolymerization reactor be equipped to operate at elevated pressuresufficient to maintain the contents of the reactor as a fluid at thereaction temperature. In general, it is preferred to conduct thepolymerization at from 1,000 to 5,000 pounds per square inch (psi), andmore preferably at from 3,200 to 4,200 psi.

In the process of the present invention, the one or more monomers, theat least one initiator and, optionally, the one or more solvents arecombined to form a reaction mixture. The order of combining thecomponents of the reaction mixture is not critical to the process of thepresent invention. In one embodiment of the present invention, it may bedesirable to use one or more solvents, heat the one or more solvents toan elevated temperature, and add the one or more monomers and the atleast one initiator to the heated solvent to form the reaction mixture.It is preferred to add the at least one initiator last. The reactionmixture can be formed at a temperature below, at or above theoligomerzation temperature. In one embodiment of the invention, it maybe desirable to add an additional amount of one or more solvents to theoligomer product while the oligomer product is at an elevatedtemperature to maintain desirable fluidity and viscosity properties ofthe oligomer product.

The reaction mixture may optionally contain metal ions, such as copper,nickel or iron ions or combinations thereof.

The process of the present invention generally results in a relativeconversion of the monomers into oligomer product of from 10 to greaterthan 95 percent relative to the initial amount of the one or moremonomers present in the reaction mixture. If residual monomer levels inthe oligomer mixture are unacceptably high for a particular application,their levels can be reduced by any of several techniques known to thoseskilled in the art. Preferably, any residual monomers which may bepresent in the oligomer mixture are distilled or "stripped" and recycledfor later use.

The process of the present invention results in oligomers having lowmolecular weights and narrow polydispersities. Furthermore, selectedembodiments of the process result in products which do not require theremoval of organic solvents and are not contaminated with high levels ofsalt. The process of the present invention can be used to produceoligomers having number average molecular weights below 5,000,preferably below 3,000, and most preferably from 200 to 1,000. Theprocess of the present invention is useful for producing oligomers ofthe structural formula shown above wherein the sum of m and n is lessthan or equal to 50, preferably less than 20, most preferably less than10.

In a preferred embodiment of the present invention, the oligomer productis predominantly a mixture of terminally unsaturated dimers, terminallyunsaturated trimers and terminally unsaturated tetramers. Dimers areoligomeric products of formula (I) wherein the sum of n and m is 1;trimers are oligomeric products of formula (I) wherein the sum of n andm is 2; tetramers are oligomeric products of formula (I) wherein the sumof n and m is 3. The oligomer product preferably contains from 5 to 95percent of terminally unsaturated dimer, more preferably from 15 to 80percent of terminally unsaturated dimer based on the total weight ofoligomer product in the oligomer mixture. The oligomer productpreferably contains from 5 to 95 percent of terminally unsaturatedtrimer, more preferably from 15 to 80 percent of terminally unsaturatedtrimer based on the total weight of oligomer product in the oligomermixture. The oligomer product preferably contains from 0 to 90 percentof terminally unsaturated tetramer, more preferably from 5 to 70 percentof terminally unsaturated tetramer based on the total weight of oligomerproduct in the oligomer mixture.

The oligomers prepared by the process of the present invention may beused, for example, as additives for detergents, including, for example,powdered laundry detergents, liquid laundry detergents, automaticmachine dishwashing detergents, hand dishwashing detergents andcleaners. The oligomers may also be used as water-treatment additives orscale inhibitors. The oligomers may also be used, for example, asdispersants for pigments, minerals, clays, cosmetics, and formulatedproducts such as soaps or agricultural chemical formulations. Theoligomers may also be used as a soil humectant to prevent soil fromdrying and eroding.

When the terminally unsaturated oligomers of the present inventioncontain, for example, a carboxylic acid group, the oligomers can be reacted with polyfunctional alcohols having two or more alcoholfunctionalities to form polyesters. Suitable polyfunctional alcoholsinclude, for example, diols, triols and other polyols. Examples ofsuitable polyfunctional alcohols include, for example, sugars, glycerol,polysaccharides, polyvinyl alcohols), ethylene glycol, propylene glycol,polyethylene glycol) and polypropylene glycol). Preferably, thepolyfunctional alcohol is ethylene glycol, sorbitol, sucrose, glucose ora mono-, oligo- or polysaccharide. The reaction of terminallyunsaturated oligomers containing carboxylic acid groups withpolyfunctional alcohols can be conducted in any suitable manner and ispreferably conducted in the presence of an acid catalyst.

Similarly, when the terminally unsaturated oligomers of the presentinvention contain at least one carboxylic acid group, the at least onecarboxylic acid group can undergo a condensation re action with anysuitable amine to form a compound which is an amide, polyamide orpolyester amide). Also, any suitable amine can undergo a Michael-typeaddition to the terminally unsaturated moiety of the terminallyunsaturated oligomer to form a compound which is a Michael adduct, whichmay also undergo a reaction to form a compound which is an amide,polyamide or poly(ester amide). Suitable amines, include for example,amino acids, alkylamines, diamines, triamines and alkanolamines.Particular examples of suitable amines include ammonia, methylamine,lysine, ethylenediamine, ethanolamine and Jeffamines sold by Exxon Corp.

Polyesters, amides, polyamides, poly(ester amides) or Michael adductcontaining, as reacted units, the terminally unsaturated oligomers, areuseful, for example, as additives for detergents, including, forexample, powdered laundry detergents, liquid laundry detergents,automatic machine dishwashing detergents, hand dishwashing detergentsand cleaners, as water-treatment additives or scale inhibitors, asdispersants for pigments, minerals, clays, cosmetics, and formulatedproducts such as soaps or agricultural chemical formulations.

Because the oligomers are terminally unsaturated, they can also be used,for example, as monomers in a subsequent polymerization, such as in abulk polymerization, solution polymerization, emulsion polymerization,or suspension polymerization. The terminally unsaturated oligomers canbe subsequently polymerized with themselves to form a homopolymer, orwith one or more other ethylenically unsaturated monomers to formcopolymers. The polymers resulting from the subsequent polymerization ofthe terminally unsaturated oligomers of the present invention may beuseful, for example, in the same applications as the oligomers, or asadhesives, coatings, surfactants, adsorbents, ion-exchange resins andother polymeric applications.

The terminally unsaturated oligomers can also be grafted onto anysuitable substrate. Compounds which are suitable substrates are thosewhich contain hydrogen atoms which can be abstracted by a free-radical.Examples of suitable substrates include: polyhydric alcohols such assugars, glycerol, polysaccharides, and poly(vinyl alcohol);poly(ethylene glycol); poly(propylene glycol); and certain esters suchas polycaprolactone. Preferably, the graft substrate is poly(ethyleneglycol) (PEG), sorbitol, sucrose, glucose, or other mono-, oligo- orpolysaccharide.

THE EOUIPMENT AND GENERAL PROCEDURE

A 10 foot long section of titanium tubing having an inner diameter of1/16th inch and a wall thickness of 0.050 inch was connected at one endto a high pressure pump (Hewlett Packard Model HP 1050 TI) and atanother end to a back-pressure control device. Between the two ends, thesection of tubing was coiled about a torus-shaped metal mandrel. Themandrel was situated above a primary coil of a transformer so that thecoils of titanium tubing and the mandrel functioned as secondary coilsof the transformer. The coils of titanium tubing were further equippedwith one end of a temperature probe. The other end of the temperatureprobe was connected to a temperature controlling device. The temperaturecontrolling device regulated the current supplied to the primary coil ofthe transformer which had the effect of regulating the heat ofinductance imparted to the coiled steel tubing.

A reaction mixture was prepared by mixing solvent, monomer, andinitiator. Helium was bubbled through the mixture while stirring.

Deionized water was pumped through the tubing via the high pressure pumpat a rate of from 0.05 to 10 milliliters per minute ("ml/min"). Thepressure was maintained at a level of from 3300 to 5000 pounds persquare inch ("psi"). Current was supplied to the primary coil of thetransformer to increase the temperature within the tubing to the desiredpolymerization temperature. After about 15 minutes, the water beingpumped through the tubing was replaced by the reaction mixture which wascontinuously pumped through the tubing at the same rate, temperature andpressure. After allowing a suitable amount of time for the water to becleared from the tubing, product was collected as the effluent from theback-pressure control device. When the reaction mixture was nearly gone,deionized water was pumped through the tubing at the same rate, pressureand temperature as the reaction mixture.

The molecular weights referred to are measured by gel permeationchromatography using a polyacrylic acid standard unless specificallystated otherwise. Terminal unsaturation was detected and measured byboth ¹ H NMR spectroscopy and ¹³ C NMR spectroscopy. Conversion wasmeasured as a function of product solids, and was also determined byresidual monomer analysis using high pressure liquid chromotagraphy.

EXAMPLES 1-6

Examples 1-6 are oligomerizations conducted according to the generalprocedure outlined above. The reaction mixture was a 5 percent by weightaqueous solution of glacial acrylic acid and 1 percent by weight basedon the weight of glacial acrylic acid of 90 percent by weighttert-butylhydroperoxide. The flow rate was adjusted to provide aresidence time of 16 seconds. The polymerization temperature ("Temp."),percent "Conversion" of monomer to oligomer, M_(w) and M_(n) appear inbelow. Analysis of the oligomer product, where formed, indicated thatthe oligomers were terminally unsaturated oligomers.

                  TABLE I    ______________________________________    Example  Temp. (° C.)                       Conversion (%)                                    M.sub.w                                         M.sub.n    ______________________________________    1        250       30           1356 696    2        275       40           963  504    3        300       48           588  390    4        325       43           479  325    5        350       41           396  273    6        375       42           342  235    ______________________________________

The data in Table I show that terminally unsaturated oligomers wereformed in polymerizations conducted at a temperature above 200° C. Thedata also show that the M_(w) and M_(n) decrease as temperatureincrease.

EXAMPLES 7-14

Examples 7-14 are polymerizations conducted according to the generalprocedure outlined above using the same conditions as Examples 1-6except that the initiator was hydrogen peroxide. The polymerizationtemperature ("Temp."), percent "Conversion" of monomer to oligomer, Mwand Mn appear in Table II below. Analysis of the oligomer productindicated that the oligomers were terminally unsaturated oligomers.

                  TABLE II    ______________________________________    Example Temp. (° C.)                       Conversion (%)                                   M.sub.w                                         M.sub.n    ______________________________________     7      200         8          >4400 >3600     8      225        11          3354  2019     9      250        17          1762  986    10      275        29          1110  664    11      300        48           796  520    12      325        58           641  438     13*    350        --           508  339    14      375        60           439  307    ______________________________________     *The residence time for Example 13 was 45 seconds

The data in Table II show that terminally unsaturated oligomers wereformed in polymerizations conducted at a temperature at, and above, 200°C. The data also show that the M_(w) and M_(n) decrease as temperatureincrease and that conversion increases as temperature increases. Thedata also show that hydrogen peroxide is a initiator.

EXAMPLES 15-24

Examples 15-24 are polymerizations conducted according to the generalprocedure outlined above using the same conditions as Examples 1-6except that the residence time was 24 seconds. The initiator type("Initiator"), polymerization temperature ("Temp."), percent"Conversion" of monomer to oligomer, Mw and Mn appear in Table IIIbelow. Analysis of the oligomer product indicated that the oligomerswere terminally unsaturated oligomers.

                  TABLE III    ______________________________________    Example Initiator                    Temp. (° C.)                               Conversion (%)                                        M.sub.w                                              M.sub.n    ______________________________________    15      t-BHP   350        54       510   358    16      H.sub.2 O.sub.2                    350        68       508   339    17      t-BHP   375        50       436   327    18      H.sub.2 O.sub.2                    375        60       427   308    19      t-BHP   390        48       435   317    20      H.sub.2 O.sub.2                    390        56       396   294    21      t-BHP   410        44       400   307    22      H.sub.2 O.sub.2                    410        44       376   285    23      t-BHP   425        42       392   301    24      H.sub.2 O.sub.2                    425        40       360   282    ______________________________________

The data in Table III show that the Mw and Mn decrease as temperatureincreases, and that the polymerizations can be conducted at atemperature of at least 425° C,

EXAMPLES 25-41

Examples 25-41 are polymerizations conducted according to the generalprocedure outlined above using the same conditions as Examples 1-6except the residence time was 8 seconds the concentration, in percent byweight, of the aqueous acrylic acid solution was the percent shown inTable IV below as "AA Level"; the initiator was at a level shown inTable IV below ("Init. Level" reported as the percent by weight based onthe weight of acrylic acid); the temperature for each of thepolymerizations shown in Table IV below was 375° C. Analysis of theoligomer product indicated that the oligomers were terminallyunsaturated oligomers.

                  TABLE IV    ______________________________________    Example AA Level Init. Level                               Conversion (%)                                        M.sub.w                                              M.sub.n    ______________________________________    25       5       5         70        611  279    26       5       3         64        373  223    27       5       1         43        317  221    28      15       1         60        954  374    29      15       3         84        975  360    30      15       5         89        987  360    31      30       1         81       1842  502    32      30       3         92       1797  482    33      30       5         94       1795  476    34      50       1         86       2369  581    35      50       3         95       2252  536    36      50       5         96       2169  527    ______________________________________

EXAMPLES 37-40

Examples 37-40 are polymerizations conducted according to the generalprocedure outlined above using the same conditions as Examples 1-6except no initiator was used and the residence time was 46 seconds. Thepolymerization temperature ("Temp.") and observations appear in Table V,below.

                  TABLE V    ______________________________________    Example  Temp (° C.)                          Observations    ______________________________________    37       250          no oligomer formation observed    38       325          no oligomer formation observed    39       375          no oligomer formation observed    40       425          no oligomer formation observed    ______________________________________

The data in Table V show that no oligomer was formed in the absence ofinitiator.

EXAMPLES 41-46

Examples 41-46 are polymerizations conducted according to the generalprocedure outlined above using the same conditions as Examples 1-6except the concentration, in percent by weight, of the aqueous acrylicacid solution was 2.5 percent; the reaction mixture contained an equalamount of methacrylic acid (based on the weight of acrylic acid); thetubing was made of stainless steel. The polymerization temperature("Temp."), the percent of acrylic acid monomer converted to oligomerproduct (reported as "AA Conversion (%)"), the percent of methacrylicacid monomer converted to oligomer product (reported as "MAA Conversion(%)"), M_(w) and M_(n) appear in Table VI below. Analysis of theoligomer products indicated that the oligomers were terminallyunsaturated oligomers.

                  TABLE VI    ______________________________________           Temp.   AA Conversion                              MAA Conversion    Example           (° C.)                   (%)        (%)       M.sub.w                                              M.sub.n    ______________________________________    41     250     10         10        2614  977    42     275     10         16        1254  563    43     300     17         19        738   409    44     325     22         21        476   326    45     350     17         19        397   295    46     375     13         16        327   252    ______________________________________

The data in Table VI show that the process of the invention producedterminally unsaturated oligomers from a mixture of monomers.

EXAMPLES 47-52

Examples 47-52 are polymerizations conducted according to the generalprocedure outlined above using the same conditions as Examples 1-6except the concentration, in percent by weight, of the aqueous acrylicacid solution was 2.5 percent; the reaction mixture contained an equalamount of maleic acid (based on the weight of acrylic acid); the tubingwas made of stainless steel. The polymerization temperature ("Temp."),the percent of acrylic acid monomer converted to oligomer product(reported as "AA Conversion (%)"), the percent of maleic acid monomerconverted to oligomer product (reported as "MAL Conversion (%)"), M_(w)and M_(n) appear in Table VII below. Analysis of the oligomer productsindicated that the oligomers were terminally unsaturated oligomers.

                  TABLE VII    ______________________________________           Temp.   AA Conversion                              MAL Conversion    Example           (° C.)                   (%)        (%)       M.sub.w                                              M.sub.n    ______________________________________    47     250     60         58        338   251    48     275     63         62        384   260    49     300     58         58        369   250    50     325     62         62        371   256    51     350     57         57        363   246    52     375     60         60        369   247    ______________________________________

The data in Table VII show that the process of the invention producedterminally unsaturated oligomers from a mixture of monomers.

EXAMPLES 53-60

Examples 53-60 were carried out as follows: A 6 foot long section ofstainless steel tubing having an inner diameter of 1/16th inch and awall thickness of 0.050 inch was connected at one end to a high pressurepump (Hewlett Packard Model HP 1050 TI) and at another end to aback-pressure control device. Between the two ends, the section oftubing was immersed in a temperature-controlled sand bath maintained at375° C. A reaction mixture was prepared by mixing solvent, monomer, andinitiator. Solvent was pumped through the tubing via the high pressurepump at a rate of about 10 ml/min. The pressure was maintained at alevel of about 3500 psi. After about 15 minutes, the solvent beingpumped through the tubing was replaced by the reaction mixture which wascontinuously pumped through the tubing at the same rate, temperature andpressure. After allowing a suitable amount of time for the solvent to becleared from the tubing, product was collected as the effluent from theback-pressure control device.

The reaction mixtures contained various amounts of glacial acrylic acid(reported in Table VIII as "AA%" in percent by weight of acrylic acidbased on the reaction mixture) and 1 percent by weight based on theweight of glacial acrylic acid of 90 percent by weighttert-butylhydroperoxide. The reaction mixture also contained variousamounts and types of solvents (reported in Table VIII as "Water %""Other %" in percent by weight of the reaction mixture). The flow rateprovided a residence time of 14 seconds. M_(w) and M_(n) appear in TableVIII below. Analysis of the oligomer product, where formed, indicatedthat the oligomers were terminally unsaturated oligomers.

                  TABLE VIII    ______________________________________             Solvent    Example           AA %    Water %  Other %     M.sub.w                                              M.sub.n    ______________________________________    53     10      90       0           784   533    54     10      60       isopropyl alcohol, 30                                        532   377    55     20       0       isopropyl alcohol, 80                                        605   343    56     30      70       0           1443  620    57     30      20       isopropyl alcohol, 50                                        606   418    58     30       0       isopropyl alcohol, 70                                        588   355    59     30       0       acetone, 70 1087  536    60     30       0       methanol, 70                                        576   346    ______________________________________

EXAMPLE 61

The oligomer product obtained from the process similar to the process ofExample 27 was chilled in a refrigerator. A crystalline precipitateformed and was collected. Analysis by ¹ H NMR spectroscopy confirmed theidentity of the crystalline product as the terminally unsaturated dimerof acrylic acid (2-methylene glutaric acid). A reaction mixture wasformed by dissolving 0.432 grams of the terminally unsaturated dimer ofacrylic acid and 0.045 grams of ammonium persulfate in 5 milliliters ofD₂ O. The reaction mixture was heated to 80° C. while stirring. Samplesof the heated reaction mixture were analyzed by ¹ H NMR spectroscopy todetermine the conversion of the terminally unsaturated dimer into highermolecular weight polymer product after 1 hour, 2.5 hours, and 4 hours.The percent of terminally unsaturated dimer converted to highermolecular weight polymer product (reported as "Dimer Conversion (%)"),M_(w) and M_(n) of the higher molecular weight polymer product appear inTable IX below.

                  TABLE IX    ______________________________________              Dimer    Time      Conversion (%)  M.sub.w                                     M.sub.n    ______________________________________      0 hour   0               144    144      1 hour  73              n.m.*  n.m.    2.5 hours 93              4659   1480      4 hours >98             4862   1960    ______________________________________     "n.m." is not measured

The data in Table IX show that the terminally unsaturated oligomers canbe polymerized to form higher molecular weight polymers.

EXAMPLE 62

The same procedure was followed as in Example 62 except that theterminally unsaturated dimer was converted to the sodium salt withdilute aqueous sodium hydroxide before the polymerization. The dataappear in Table X below.

                  TABLE X    ______________________________________              Dimer    Time      Conversion (%)  M.sub.w                                     M.sub.n    ______________________________________      0 hour   0              144    144      1 hour  47              n.m.*  n.m.    2.5 hours 70              836    480      4 hours 82              954    612    ______________________________________     "n.m." is not measured

The data in Table X show that the terminally unsaturated oligomers canbe polymerized to form higher molecular weight polymers.

EXAMPLE 63

To a one liter, 4-neck flask equipped with a mechanical stirrer, refluxcondenser, thermometer, and inlets for the gradual addition of monomerand initiator solution was added 48.5 grams of deionized water. Thecontents of the flask were heated to 82° C. while stirring. An initiatorsolution of 3.1 grams of ammonium persulfate and 20.0 grams of deionizedwater was prepared. A monomer solution of 30 grams of terminallyunsaturated oligomers prepared in a manner similar to Example 27 havingM_(w) of 535 and M_(n) of 360 dissolved in 30 grams of deionized waterwas prepared. A neutralizer solution of 99.0 grams of 14.7% by weightaqueous sodium hydroxide was prepared. A solution of 0.5 grams ofammonium persulfate dissolved in 2 grams of water was added to the flaskimmediately prior to the addition of the monomer, initiator andneutralizer solutions which were added linearly and separately. Theneutralizer solution was added over 30 minutes, and the initiatorsolution and the monomer solution were added over 1.5 hours. Once theaddition was complete, the system was kept at 82° C. for 30 minutes. Thesystem was then cooled to ambient temperature.

The solids content of the resulting polymer solution was 20.3%, theM_(w) was 1980 and the M_(n) was 1780. The residual terminallyunsaturated oligomer was <1% based on the original amount of terminallyunsaturated oligomer.

EXAMPLE 64

To a one liter, 4-neck flask equipped with a mechanical stirrer, refluxcondenser, thermometer, and inlets for the gradual addition of monomerand initiator solution was added 15.0 grams of deionized water and 15grams of 1-propanol. The contents of the flask were heated to 82° C.while stirring. An initiator solution of 3.1 grams of ammoniumpersulfate, 10.0 grams of deionized water and 10.0 grams of 1-propanolwas prepared. A monomer solution of 18.55 grams of terminallyunsaturated oligomers prepared in a manner similar to Example 27 havingMw of 535 and Mn of 360, 15.2 grams of 2-acrylamidomethylpropanesulfonicacid, and 4.5 grams of t-butylacrylamide dissolved in 18.6 grams of1-propanol was prepared. A neutralizer solution of 20.8 grams of 50.0%by weight aqueous sodium hydroxide was prepared. A solution of 0.5 gramsof ammonium persulfate dissolved in 1 gram of water and 1 gram of1-propanol was added to the flask immediately prior to the addition ofthe monomer, initiator and neutralizer solutions which were addedlinearly and separately. The neutralizer solution was added over 30minutes, and the initiator solution and the monomer solution were addedover 1.5 hours. Once the addition was complete, the system was kept at82° C. for 30 minutes. The system was then cooled to ambienttemperature.

The solids content of the resulting polymer solution was 29.2%, the Mwwas 2249 and the Mn was 893. The residual terminally unsaturatedoligomer was <1% based on the original amount of terminally unsaturatedoligomer.

EXAMPLE 65

To a one liter, 4-neck flask equipped with a mechanical stirrer, refluxcondenser, thermometer, and inlets for the gradual addition of monomerand initiator solution was added 20.0 grams of deionized water. Thecontents of the flask were heated to 82° C. while stirring. An initiatorsolution of 3.1 grams of ammonium persulfate and 3.9 grams of deionizedwater was prepared. A monomer solution of 19.5 grams of terminallyunsaturated oligomers prepared in a manner similar to Example 27 havingM_(w) of 535 and M_(n) of 360,10.5 grams of hydroxyethylmethacrylate and20 grams of deionized water was prepared. A neutralizer solution of 2.2grams of 30.0% by weight aqueous ammonium hydroxide dissolved in 4.8grams of deionized water was prepared. A solution of 0.5 grams ofammonium persulfate dissolved in 2 grams of water was added to the flaskimmediately prior to the addition of the monomer, initiator andneutralizer solutions which were added linearly and separately. Theneutralizer solution was added over 30 minutes, and the initiatorsolution and the monomer solution were added over 1.5 hours. Once theaddition was complete, the system was kept at 82° C. for 30 minutes. Thesystem was then cooled to ambient temperature. The contents of the flaskwere neutralized 13.4 grams of 30% by weight aqueous ammonium hydroxide.

The solids content of the resulting polymer solution was 33.8%, theM_(w) was 5520 and the M_(n) was 3590. The residual terminallyunsaturated oligomer was <1% based on the original amount of terminallyunsaturated oligomer. The residual hydroxyethylmethacrylate was 355 ppmbased on the original amount of hydroxyethylmethacrylate.

EXAMPLE 66

To a one liter, 4-neck flask equipped with a mechanical stirrer, refluxcondenser, thermometer, and inlets for the gradual addition of monomerand initiator solution was added 35.0 grams of deionized water. Thecontents of the flask were heated to 80° C. while stirring. An initiatorsolution of 3.1 grams of ammonium persulfate and 20.0 grams of deionizedwater was prepared. A monomer solution of 18 grams of terminallyunsaturated oligomers prepared in a manner similar to Example 27 havingMw of 535 and Mn of 360, and 26.6 grams of2-acrylamidomethylpropanesulfonic acid dissolved in 18 grams ofdeionized water was prepared. A neutralizer solution of 20 grams of50.0% by weight aqueous sodium hydroxide was prepared. A solution of 0.5grams of ammonium persulfate dissolved in 2 grams of water was added tothe flask immediately prior to the addition of the monomer, initiatorand neutralizer solutions which were added linearly and separately. Theneutralizer solution was added over 30 minutes, and the initiatorsolution and the monomer solution were added over 1.5 hours. Once theaddition was complete, the system was kept at 80° C. for 30 minutes. Thesystem was then cooled to ambient temperature.

The solids content of the resulting polymer solution was 30.2%, theM_(w) was 4460 and the M_(n) was 3810. The residual terminallyunsaturated oligomer was <1% based on the original amount of terminallyunsaturated oligomer.

EXAMPLE 67

To a 250 milliliter, 4-neck flask equipped with a mechanical stirrer,Dean-Stark condenser, thermometer, and an inlet and an outlet fornitrogen was added 31.7 grams of terminally unsaturated oligomer ofacrylic acid (Mw of 490, Mn of 219) and 9.2 grams of ethylene glycol.The flask was immersed in an oil bath maintained at 150° C. whilestirring the contents of the flask for 6.5 hours, then allowed to coolto room temperature. To the stirred contents of the flask was added 200milliliters of deionized water and a sufficient amount of a 50 percentby weight aqueous solution of sodium hydroxide to form a homogeneoussolution. The resulting polyester had a M_(w) of 22300 and M_(n) of2030.

EXAMPLE 68

A polyester was prepared in a similar manner as Example 67 except theterminally unsaturated oligomer of acrylic acid had M_(w) of 228 andM_(n) of 167; and the flask was immersed in an oil bath maintained at170° C. while stirring the contents of the flask for 2.0 hours. Theresulting polyester had a M_(w) of 2530 and M_(n) of 1560.

EXAMPLE 69

A polyester was prepared in a similar manner as Example 68 except theethylene glycol was replaced with an equimolar amount of poly(ethyleneglycol) having M_(w) of 400. The resulting polyester had a M_(w) of 2070and M_(n) of 391.

EXAMPLE 70

A polyester was prepared in a similar manner as Example 69 except thepoly(ethylene glycol) had Mw of 1000. The resulting polyester had aM_(w) of 2150 and M_(n) of 403.

EXAMPLE 71

To a 500 milliliter three-neck flask equipped with a mechanical stirrerand reflux condenser was added 100.1 grams of terminally unsaturatedoligomer of acrylic acid (M_(w) of 184, M_(n) of 139) and 92.5 grams oflysine. The contents of the flask were heated to 150° C. for 1 hour withcontinuous stirring, then allowed to cool to room temperature. A 10 gramsample was transferred from the flask to a beaker, and the beaker wasplaced in an oven maintained at 170° C. for 2 hours with manual stirringevery 30 minutes. After 2 hours, the beaker was removed from the ovenand allowed to cool to room temperature. To the beaker was added, whilestirring, 50 milliliters of deionized water and a sufficient amount of a50 percent by weight aqueous solution of sodium hydroxide to form ahomogeneous solution. The resulting polyamide had a M_(w) of 1780 andM_(n) of 466.

EXAMPLE 72

A polyamide was prepared in a similar manner as Example 71 except thebeaker was placed in an oven maintained at 170° C. for 2.5 hours. Theresulting polyamide had a M_(w) of 6790 and M_(n) of 886.

EXAMPLE 73

A polyamide was prepared in a similar manner as Example 71 except thebeaker was placed in an oven maintained at 170° C. for 3 hours. Theresulting polyamide had a M_(w) of 12,400 and M_(n) of 962.

EXAMPLE 74

A polyamide was prepared in a similar manner as example 71 except thebeaker was placed in an oven maintained at 170° C. for 3.5 hours. Theresulting polyamide had a M_(w) of 36,600 and M_(n) of 1950.

Liquid Detergent Formulation and Performance Evaluation

The efficacy of the oligomers in a liquid detergent formulation wasevaluated by washing soiled cotton fabrics in a prototypical,ultra-heavy duty liquid laundry detergent composition utilizing SearsKenmore® Ultra Fabric Care brand washing machines (model Heavy Duty 80Series) set to typical U.S. laundering parameters. Washing conditionsare detailed in Table XI below, and the liquid detergent formulationused for the evaluations was that shown in Table XII.

Cotton cloth ("Cotton") was purchased from Test Fabrics, Inc.(Middlesex, N.J.) and cut to a specified size (31/2"×41/2"). The clothswere then soiled using a China bristle brush (#10) by applying eitherfrom 0.7 to 0.8 grams of a 25% clay slurry (in water). The soil was"painted" onto the cloth inside a 2" diameter circle and allowed to airdry overnight prior to laundering. The clays used to soil the clothswere of two types: a) a deep-orange clay (designated "Clay 1" in TableXIII, below), and b) a reddish-brown particulate clay (designated "Clay2" in Table XIII, below). In addition, cotton cloths pre-soiled withclay (designated "Clay 3" in Table XIII, below), were purchased fromScientific Services (Oakland, N.J.). The clay used by ScientificServices was a brown clay.

Cotton cloths pre-soiled with a dust/sebum mixture, cotton/polyesterblend cloths pre-soiled with a dust/sebum mixture ("PE/C"), andpolyester cloth ("PE") pre-soiled with a dust/sebum mixture were alsopurchased from Scientific Services (Oakland, N.J.).

Reflectance of each of the cloths was measured using a PacificScientific Colorimeter (Colorgard System 1000) and the data recordedusing the X,Y,Z color scale. The reflectance (Y) of the soiled clothswas measured before laundering so that only cloths of the samereflectance were used in a test. Reflectance was then measured afterlaundering to evaluate the efficacy of the detergent. The Y valuesreported in Table XIII are the reflectance values obtained afterlaundering the cloths as described above.

Each of the three clay soils were evaluated with four replicates. Thedata appearing in Table XIII are composite averages of the reflectancevalues obtained from all of the clay soils laundered with thebuilder/adjuvant listed.

                  TABLE XI    ______________________________________    WASH CONDITIONS    ______________________________________    APPARATUS     SEARS KENMORE BRAND WASHING                  MACHINE    TEMPERATURE   WARM (95° F.)    WATER HARDNESS                  MODERATE (200 ppm)    AGITATION     HIGH    WASH CYCLE    MEDIUM (10 MIN.)    WATER CAPACITY                  16.7 GALLONS/LOAD    DETERGENT DOSAGE                  100 GRAMS    ______________________________________

                  TABLE XII    ______________________________________    Component           parts by weight    ______________________________________    Surfactants    Linear Dodecylbenzene Sulfonate                        15.0    Alcohol Ethoxylate (Nonionic)                        9.5    Sodium Alcohol Ethoxysulfate                        5.0    Builder/Adjuvant    Sodium Citrate or oligomer                        12.5    Hydrotrope/Solubilizing Agent    Monoethanolamine    2.5    Triethanolamine     2.0    Propylene Glycol    2.5    Sodium Xylene Sulfonate                        5.0    ______________________________________     *Misc. and Water up until total formulation is 100 parts.     *Misc. includes perfume, colorants, fatty acids, whiteners and opacifiers

                  TABLE XIII    ______________________________________    Reflectance Values                        Reflectance (Y)            Reflectance (Y)                          Dust/Sebum soils    Builder/Adjuvant              Clay 1  Clay 2  Clay 3                                    Cotton                                          PE/C  PE    ______________________________________    none      63.5    50.8    61.5  59.7  62.1  51.6    oligomer* 65.5    52.3    65.4  61.4  64.2  53.9    (M.sub.w = 270)    oligomer* 66.0    51.4    65.9  60.5  63.7  54.2    (M.sub.w = 370)    citrate   65.5    51.5    64.0  60.1  63.7  52.6    ______________________________________     *terminally unsaturated oligomer of acrylic acid prepared in a similar     manner as Example 6.

These results demonstrate that the terminally unsaturated oligomersproduced by the present invention are effective as additives, andpotential partial or complete replacements for citrate, in liquidlaundry detergents.

Powder Detergent Formulation and Performance Evaluation

The efficacy of the oligomers and polymers containing the oligomers aspolymerized units were evaluated in a powder detergent formulation bywashing soiled cotton and cotton/terry blended fabrics in aprototypical, powdered laundry detergent composition shown in Table XV,below. Cloths were stained in the manner described above. The clay usedto soil the cloths was a reddish-brown particulate clay.

The detergent compositions were tested in a Terg-o-Tometer at thefollowing conditions; 40° C., 100 rpm, 100 ppm hardness (50% city tapwater/50% de-ionized water), 12 minute wash with one 3 minute rinse,1300 ppm detergent and 5 cloths per pot (3 of them soiled). The washwater was pre-heated, the fabric swatches were added and then dissolveddetergent (2.6 grams of a 50% slurry in 100 milliliters water) wasadded. Following the wash period the swatches were wrung, and followingthe rinse cycle the swatches were wrung again and then air dried.Swatches washed in a detergent containing no polymer or oligomer werealways run as a control.

Reflectance was measured using a Pacific Scientific Colorimeter(Colorgard System 1000) and the data recorded using the L,a,b colorscale. Detergency values (E), a measure of soil removal, and whitenessindex (W.I.), a measure of anti-redeposition, are calculated as:

    E=((L.sub.s -L).sup.2 +(a.sub.s -a).sup.2 +(b.sub.s -b).sup.2).sup.0.5

    W.I.=(L/100)*(L-(5.715*b))

where L_(s), a_(s), and b_(s) are the reflectivity reading for thesoiled swatches and L,a,b are the reflectivity readings for the washedswatches. Each polymer was evaluated in three separate washingexperiments. The detergent composition and levels of the components inparts by weight ("pbw") are shown in Table XV. This composition was usedfor the above described performance evaluation and the results of thedetergent performance evaluation are listed in Table XVI. Thereflectance of the soiled cloths was measured before laundering so thatonly cloths of the same reflectance were used in a test. Reflectance wasthen measured after laundering to evaluate the efficacy of the polymerin the detergent. The values reported in Table XVI are the average ofthe change in detergency and whiteness index of three cloths relative tothe control cloths laundered in detergent not containing polymer.Positive numbers indicate an increase in detergency or whiteness index.

                  TABLE XIV    ______________________________________    WASH CONDITIONS    ______________________________________    APPARATUS       Terg-o-tometer washing machine    AGITATION       100 revolutions per minute    TEMPERATURE     40° C.    WATER HARDNESS  100 parts per million ("ppm")    WASH CYCLE      12 minutes    RINSE CYCLE     3 minutes    WATER LEVEL     1 liter    DETERGENT DOSAGE                    1,300 ppm    BALLAST         5 cloths per load (3 soiled/2 unsoiled)    ______________________________________

                  TABLE XV    ______________________________________    Experimental Powdered Detergent Composition    Detergent Component pbw    ______________________________________    sodium carbonate    40.0    zeolite A           28.2    sodium silicate      4.9    LAS                  7.4    lauryl sulfate      14.5    oligomer, polymer, polyester                        0 or 5.0    or polyamide    ______________________________________

                  TABLE XVI    ______________________________________    Product of Example #                   Detergency (E)                              Whiteness Index    ______________________________________    none           0          0     67*           2.4        16.6    67             3.6        25.7     68*           1.1        11.8    68             2.6        14.4    69             1.8        18.2    70             1.2        11.3     71*           1.1        11.8    71             2.8        17.9    72             3.4        27.8    73             2.2        15.5    74             2.7        22.0    ______________________________________     *The oligomer starting material was tested.

Test of Terminally Unsaturated Oligomers as Inorganic PigmentDispersants

EXAMPLES 75 and 76

The slurries appearing in Table XVII, below, were made in the followingway: 0.842 grams of dispersant and 0.689 grams of sodium carbonate wereadded to deionized water and diluted with additional deionized water to210.0 grams. This mixture was stirred with a spatula until it wascompletely mixed. Then, 490.0 grams of dried clay was added to themixture and the mixture was stirred at high speed on a Waring blenderfor five minutes to provide a 70 percent by weight dispersed slurry ofclay with a "Dispersant Level" of 0.172 percent by weight based on theweight of clay. The viscosity of the slurry was then measured at 23° C.using a Brookfield viscometer, model RVT, spindle #2 at 20 rpm (reportedin Table XVII as "Initial Viscosity" in centipoises ("cps")). The slurrywas then allowed to stand for 2 weeks at 70° C. and the viscosity wasmeasured in the same manner (reported in Table XVII as "Heated AgedViscosity" in cps).

EXAMPLES 77 and 78

Slurries were prepared in a similar manner as Examples 75 and 76 except0.876 grams of dispersant and 0.717 grams of sodium carbonate were usedto provide a slurry of clay with a Dispersant Level of 0.178 percent byweight based on the weight of clay.

In Table XVII, below, Dispersant Type A is the sodium salt of aterminally unsaturated oligomer of acrylic acid having M_(w) of 1076,and Dispersant Type B is the sodium salt of a homopolymer of acrylicacid having M_(w) of 1,000.

                  TABLE XVII    ______________________________________            Dispersant                     Dispersant                              Initial Viscosity                                        Heat Aged    Example Type     Level    (cps)     Viscosity (cps)    ______________________________________    75      A        0.172    410       1090    76      B        0.172    482       1440    77      A        0.178    484       790    78      B        0.178    920       1830    ______________________________________

The data in Table XVII show that terminally unsaturated oligomers areeffective as dispersants of inorganic pigments as shown by the lowerviscosities of slurries containing them relative to slurries containingknown polymeric dispersants, both immediately after the dispersed slurryis prepared and after the slurry has been heated and aged.

We claim:
 1. A detergent composition comprising a terminally unsaturatedoligomer of the formula: ##STR6## wherein N is a residue of the formula##STR7## wherein X₁ and X₂ are independently selected from the groupconsisting of H, NH₄, alkali metals and alkaline earth metals;wherein Mis the residue of a monoethylenically unsaturated monomer; wherein m is0 to 47; wherein n is 2 to 50; and wherein the sum of n and m is lessthan or equal to
 50. 2. A detergent composition comprising a polymercomprising, as polymerized units, a terminally unsaturated oligomer ofthe formula: ##STR8## wherein N is a residue of the formula ##STR9##wherein X₁ and X₂ are independently selected from the group consistingof H, NH₄, alkali metals and alkaline earth metals;wherein M is theresidue of a monoethylenically unsaturated monomer; wherein m is 0 to47; wherein n is 2 to 50; and wherein the sum of n and m is less than orequal to
 50. 3. A dispersant composition comprising a terminallyunsaturated oligomer of the formula: ##STR10## wherein N is a residue ofthe formula ##STR11## wherein X₁ and X₂ are independently selected fromthe group consisting of H, NH₄, alkali metals and alkaline earthmetals;wherein M is the residue of a monoethylenically unsaturatedmonomer; wherein m is 0 to 47; wherein n is 2 to 50; and wherein the sumof n and m is less than or equal to
 50. 4. A dispersant compositioncomprising a polymer comprising, as polymerized units, a terminallyunsaturated oligomer of the formula: ##STR12## wherein N is a residue ofthe formula ##STR13## wherein X₁ and X₂ are independently selected fromthe group consisting of H, NH₄, alkali metals and alkaline earthmetals;wherein M is the residue of a monoethylenically unsaturatedmonomer; wherein m is 0 to 47; wherein n is 2 to 50; and wherein the sumof n and m is less than or equal to 50.